Coated substrates, organometallic films and methods for applying organometallic films to substrates

ABSTRACT

A coated article comprising a substrate having a plastic surface and adhered thereto an organometallic film in which the metal has f electron orbitals or is niobium is disclosed. Also disclosed are methods for applying organometallic films to substrates and the organometallic films themselves.

CROSS REFERENCE TO RELATED APPLICATION

The present application claims priority from U.S. Provisional PatentApplication Ser. No. 60/859,194, filed Nov. 15, 2006.

FIELD OF THE INVENTION

The present invention relates to polymer substrates coated with anorganometallic film, to organometallic films and to methods for applyingorganometallic films to substrates.

BACKGROUND OF THE INVENTION

Self-assembled films or layers on various substrates are well known inthe art. These films or layers typically have functional groups (headgroups) that bond to a cofunctional group on the substrate surface andorgano groups that have some mutual attraction to neighboring moleculesin the layer(s) or to the surface. The self-assembled films are used invarious applications such as for medical and electrical use. In medicalapplications, the self-assembled films are used to form an interfaciallayer between a titanium orthopedic implant and the surrounding bodytissue. For electrical applications, the self-assembled films are usefulfor improving the performance of devices that incorporateorganic-inorganic interfaces such as those found in organiclight-emitting diodes. An example of a self-assembled organic layer isdisclosed in U.S. Pat. No. 6,645,644 in which an organometallic compoundsuch as a titanium or zirconium metal alkoxide is applied to a substratesuch as a metal having a native oxide surface. The alkoxide groups reactwith the oxide groups forming a secure surface bond. The free orunreacted alkoxide groups are available for reaction with reactivegroups such as acid groups in a subsequently applied layer.

Unfortunately, such organometallic coatings often have poor durabilityand are easily removed from many substrates, particularly polymersubstrates such as polycarbonates and polysiloxanes.

It would be desirable to provide an organometallic coating derived froma transition metal alkoxide that has better durability and adhesion tovarious substrates, particularly polymer substrates.

SUMMARY OF THE INVENTION

The present invention provides a coated article comprising:

-   -   (a) a polymer substrate and adhered to the substrate surface    -   (b) an organometallic film in which the metal has electrons in        the f orbital or is niobium.

The organometallic film adheres well to various surfaces includingpolymer surfaces and also adheres well to subsequently applied coatingssuch as hydrophobic coatings.

The organometallic film can act as an anchor for functional coatings(e.g. hydrophobic, antifog, antistatic, conductive, etc.), or as anadhesion promoter at organic/organic, organic/inorganic interfaces (e.g.as an adhesion promoter at a polyimide/polyester interface).

The present invention also provides a method for depositing anorganometallic coating or film to a substrate comprising:

-   -   (a) contacting the surface of the substrate with a metal        alkoxide in which the metal has electrons in the f orbital or is        niobium so as to deposit a film on the surface,    -   (b) exposing the film to conditions sufficient to form a        polymeric metal oxide with alkoxide and hydroxyl groups.

The present invention also provides for organometallic films comprisingpolymer metal oxides with alkoxide and hydroxyl groups and in which themetal has electrons in the f orbital or is niobium.

DETAILED DESCRIPTION

Examples of substrates are those which have groups on their surface thatare reactive with functional groups associated with the organometalliccoating. Examples of such groups are oxide and/or hydroxyl groups.Examples of other groups are carbonyl, carbonate and amide. Non-limitingexamples of such substrates are those which inherently have such groupson their surface or which form such groups by subsequent treatment suchas exposure to the environment or a plasma treatment. Examples ofmaterials which form metal oxide surfaces upon exposure to ambientconditions include steels, including stainless steels, iron, and metalswhich acquire a non-ablating oxide coating upon exposure to the ambientenvironment, for example, tantalum, titanium, titanium alloys, aluminum,and aluminum alloys. Additional examples of materials that acquire anoxide layer upon exposure to the ambient conditions are ceramicmaterials, for example, silicon nitride. Also suitable in the method ofthe present invention are materials which have an oxide coating impartedto them, for example, thick film oxide insulators in semiconductingdevices, and those which can be derivatized to have an oxide surface,for example, gallium arsenide, gallium nitride, and silicon carbide.Other examples include conducting oxides, such as indium tin oxide,deposited on a glass substrate. Also, metal oxides can be deposited onpolymer substrates, for example, “stacked” metal oxides on polymersubstrates to provide anti-reflective properties. Examples of polymersubstrates are those that contain OH or oxide groups, such as acryliccopolymers made from one or more monomers that contain hydroxyl groups.Also, composite inorganic/organic polymers such as organo polymerscontaining entrained silica and/or alumina may be used. Surprisingly, ithas been found that certain polymers that do not adhere well toorganometallic coatings such as the titanium and zirconiumorganometallic coatings in the aforementioned U.S. Pat. No. 6,645,644adhere very well to the organometallic coatings of the presentinvention. Examples of such polymers are polycarbonates includingaromatic and aliphatic polycarbonates, polyurethanes, polyesters,polyepoxides, acrylic polymers and copolymers (without hydroxyl groups)and polysiloxanes. The polymer can be in the form of a polymer substrateor a polymer coating on a different substrate, for example, a metal ormetal oxide with a polymer surface coating, and a polycarbonatesubstrate such as an ophthalmic lens with a polysiloxane hard coat onits surface.

Preferably, the polymer surface is oxidized such as by subjecting thepolymer to an atmospheric plasma treatment in the presence of air beforeapplication of the organometallic coating.

The organometallic film or coating that is applied to the substrate isderived from an organo metal in which the metal has electrons in the felectron orbital such as metals selected from Period 6 of the PeriodicTable of elements (lanthanide series). Examples of suitable metalsinclude La, Hf, Ta, and W, with Ta being preferred. An example ofanother suitable metal is niobium. The organo portion of the metal ispreferably an alkoxide containing from 1 to 18, preferably 2 to 8 carbonatoms such as ethoxide, propoxide, isopropoxide, butoxide, isobutoxideand tertiary butoxide. The alkoxides may be in the form of simple estersand polymeric forms of the esters. For example, with the preferred metalTa, the simple esters would be Ta(OR)₅ where R is C₁ to C₁₈ alkyl.Polymeric esters would be obtained by condensation of the alkyl estersmentioned above and typically would have the structureRO—[Ta(OR)₃—O—]_(x)R where R is defined above and x is a positiveinteger. Besides alkoxides, other ligands can be present such as acetylacetonates. Also, ligands such as chloride, acetylacetonate,alkanolamine and lactate, etc. may be present.

The organometallic compound may be used neat and applied under vacuum,by chemical vapor deposition techniques, or it may be dissolved ordispersed in a diluent and applied by coating techniques describedbelow. Examples of suitable diluents are alcohols such as methanol,ethanol and propanol, aliphatic hydrocarbons, such as hexane, isooctaneand decane, ethers, for example, tetrahydrofuran and dialkylethers suchas diethylether.

Also, adjuvant materials may be present in the organometalliccomposition. Examples include stabilizers such as sterically hinderedalcohols and acids, surfactants and anti-static agents. The adjuvants ifpresent are present in amounts of up to 30 percent by weight based onthe non-volatile content of the composition.

The concentration of the organometallic compound in the composition isnot particularly critical but is usually at least 0.01 millimolar,typically from 0.01 to 100 millimolar, and more typically from 0.1 to 50millimolar.

The organometallic treating composition can be obtained by mixing all ofthe components at the same time with low shear mixing or by combiningthe ingredients in several steps. The organometallic compounds arereactive with moisture, and care should be taken that moisture is notintroduced with the diluent or adjuvant materials and that mixing isconducted in a substantially anhydrous atmosphere.

The organometallic composition can be applied to the substrate surfaceby conventional means such as immersion coating such as dipping,rolling, spraying or wiping to form a film. The diluent is permitted toevaporate. This can be accomplished by heating to 50-200° C. or bysimple exposure to ambient temperature, that is, from 20-25° C. It isbelieved that the resulting film is in the form of a polymeric metaloxide in multilayer form with unreacted alkoxide and hydroxyl groups.This is accomplished by depositing the film under conditions resultingin hydrolysis and self-condensation of the alkoxide. These reactionsresult in a polymeric coating being formed that provides cohesivestrength to the film. The conditions necessary for these reactions tooccur is to deposit the film in the presence of water, such as amoisture-containing atmosphere. The resulting film has some unreactedalkoxide groups and/or hydroxyl groups for subsequent reaction andpossible covalent bonding with an overlayer material. However, forreadily co-reactive groups, ambient temperatures, that is, 20° C., maybe sufficient. Although not intending to be bound by any theory, it isbelieved the polymeric metal oxide is of the structure:

[M(O)_(x)(OH)_(y)(OR)_(z)]_(n)

where M is the metal of the invention, R is an alkyl group containingfrom 1 to 30 carbon atoms; x+y+z=V, the valence of M; x is at least 1, yis at least 1, z is at least 1; x=V−y−z; y=V−x−z; z=V−x−y; n is greaterthan 2, such as 2 to 1000.

For optical applications, the resulting film typically has a thicknessof 5 to 100 nanometers. For other applications, thicker films can beused. When the organometallic compound is used neat and applied bychemical vapor deposition techniques in the absence of moisture, a thinmetal alkoxide film is believed to form. Polymerization, if any occurs,is minimized and the film may be in monolayer configuration. When theorganometallic compound is subjected to hydrolysis and self-condensationconditions as mentioned above, thicker films are formed.

The process of the present invention can be used to provide a film orlayer that is continuous or discontinuous, that is, in a pattern on thesubstrate surface. Non-limiting examples include spraying thecomposition onto the surface of the substrate in pre-determined areas,for example, by ink-jet printing or stenciling. Other methods may befound by adapting printing techniques, including stamping, lithographingand gravure printing a coating solution onto the substrate in a pattern.

As mentioned above, an overlayer or a different film can be applied tothe organometallic film. Such an overlayer material preferably containsgroups that are reactive with the alkoxide and/or hydroxyl groups, suchas hydroxyl groups or acid groups or derivatives thereof.

Preferably, the overlayer is an organic acid or a derivative thereof.The acid may be a carboxylic acid, a sulfonic acid or a phosphorus acid,such as a phosphoric acid, phosphonic acid or a phosphinic acid. Byderivatives of acids are meant functional groups that perform similarlyas acids such as acid salts, acid esters and acid complexes. The organogroup of the acid may be monomeric, oligomeric or polymeric. Forexample, the organo acid may be a monomeric, phosphoric, phosphonic orphosphinic acid.

Examples of monomeric phosphoric acids are compounds or a mixture ofcompounds having the following structure:

(RO)_(x)P(O)(OR′)_(y)

wherein x is 1-2, y is 1-2 and x+y=3, R is a radical having a total of1-30, preferably 6-18 carbons, where R′ is H, a metal such as an alkalimetal, for example, sodium or potassium, alkyl including substitutedalkyl having 1 to 50 carbons, preferably 1 to 4 carbons such as methylor ethyl, including substituted aryl having 6 to 50 carbons; preferably,a portion of R′ is H. The organic component of the phosphoric acid (R)can be aliphatic (e.g., alkyl having 2-20, preferably 6-18 carbon atoms)including an unsaturated carbon chain (e.g., an olefin), or can be arylor aryl-substituted moiety.

Example of monomeric phosphonic acids are compounds or mixture ofcompounds having the formula:

wherein x is 0-1, y is 1, z is 1-2 and x+y+z is 3. Preferably, R and R″are each independently a radical having a total of 1-30, preferably 6-18carbons. R′ is H, a metal, such as an alkali metal, for example, sodiumor potassium or an amine or alkyl including substituted alkyl having 1to 50 carbon atoms, preferably lower alkyl having 1-4 carbons such asmethyl or ethyl, or aryl including substituted aryl having 6 to 50carbons. Preferably at least a portion of R′ is H. The organic componentof the phosphonic acid (R and R″) can be aliphatic (e.g., alkyl having2-20, preferably 6-18 carbon atoms) including an unsaturated carbonchain (e.g., an olefin), or can be an aryl or aryl-substituted moiety.

Example of monomeric phosphinic acids are compounds or mixture ofcompounds having the formula:

wherein x is 0-2, y is 0-2, z is 1 and x+y+z is 3. Preferably, R and R″are each independently radicals having a total of 1-30, preferably 6-18carbons. R′ is H, a metal, such as an alkali metal, for example, sodiumor potassium or an amine or alkyl including substituted alkyl having 1to 50 carbon atoms, preferably lower alkyl having 1-4 carbons, such asmethyl or ethyl, or aryl including substituted aryl having 6 to 50carbons. Preferably a portion of R′ is H. The organic component of thephosphinic acid (R, R″) can be aliphatic (e.g., alkyl having 2-20,preferably 6-18 carbon atoms) including an unsaturated carbon chain(e.g., an olefin), or can be an aryl or aryl-substituted moiety.

Examples of organo groups which may comprise R and R″ include long andshort chain aliphatic hydrocarbons, aromatic hydrocarbons andsubstituted aliphatic hydrocarbons and substituted aromatichydrocarbons. Examples of substituents include carboxyl such ascarboxylic acid, hydroxyl, amino, imino, amido, thio, cyano, and fluoro.

Representative of the organophosphorous acids are as follows: aminotrismethylene phosphonic acid, aminobenzylphosphonic acid, 3-aminopropyl phosphonic acid, O-aminophenyl phosphonic acid, 4-methoxyphenylphosphonic acid, aminophenylphosphonic acid, aminophosphonobutyric acid,aminopropylphosphonic acid, benzhydrylphosphonic acid, benzylphosphonicacid, butylphosphonic acid, carboxyethylphosphonic acid,diphenylphosphinic acid, dodecylphosphonic acid, ethylidenediphosphonicacid, heptadecylphosphonic acid, methylbenzylphosphonic acid,naphthylmethylphosphonic acid, octadecylphosphonic acid, octylphosphonicacid, pentylphosphonic acid, phenylphosphinic acid, phenylphosphonicacid, bis-(perfluoroheptyl) phosphinic acid, perfluorohexyl phosphonicacid, styrene phosphonic acid, dodecyl bis-1,12-phosphonic acid,poly(hexafluoropropyl)phosphonic acid.

In addition to the monomeric organophosphorous acids, oligomeric orpolymeric organophosphorous acids resulting from self-condensation ofthe respective monomeric acids may be used.

To provide hydrophobic properties to the overlayer, the organic acid orderivative thereof is preferably a fluorinated material, typically aperfluorinated oligomer having a number average molecular weight of lessthan 2000. The perfluorinated material can be a perfluorinatedhydrocarbon of the following structure:

R_(f)—(CH₂)_(p)—X

where R_(f) is a perfluorinated alkyl group or a perfluorinated alkyleneether group and p is 2 to 4, preferably 2.

Examples of perfluoroalkyl groups are those of the structure:

where Y is F or C_(n)F_(2n+1); m is 4 to 20 and n is 1 to 6.

Examples of perfluoroalkylene ether groups are those of the structure:

where A is an oxygen radical or a chemical bond; n is 1 to 6; Y is F orC_(n)F_(2n+1); W is H, F, C_(n)H_(2n) or C_(n)F_(2n); b is 2 to 10, m is0 to 6, and p is 0 to 18.

X is an acid group or an acid derivative. Preferably, X is:

where R and R″ are a hydrocarbon or substituted hydrocarbon radicalhaving up to 200, such as 1 to 30 and 6 to 20 carbons, R can alsoinclude the perfluoroalkyl groups mentioned above, and R′ is H, a metalsuch as potassium or sodium or an amine or an aliphatic radical, forexample, alkyl including substituted alkyl having 1 to 50 carbons,preferably lower alkyl having 1 to 4 carbons such as methyl or ethyl, oraryl including substituted aryl having 6 to 50 carbons.

Examples of fluorinated materials are esters of perfluorinated alcoholssuch as the alcohols of the structure:

where Y is F or C_(n)F_(2n+1); m is 4 to 20 and n is 1 to 6.

Examples of suitable esters are stearates and citrates of such alcohols.Such materials are available from E. I. du Pont de Nemours and Companyunder the trademark ZONYL FTS and ZONYL TBC.

For application to the surface of the substrate, the overlayer materialis dissolved in a liquid diluent. The concentration of the overlayermaterial is typically dilute, for example, no greater than 10 percent ona weight/volume basis for solid overlayer material and 10 percent on avolume/volume basis for oil and liquid overlayer material, andpreferably is within the range of 0.01 to 1.0 percent. The percentagesare based on total weight or volume of the solution.

Examples of suitable diluents are hydrocarbons such as hexane isooctaneand toluene; ketones such as methyl ethyl ketone; alcohols such asmethanol and ethanol; ethers such as tetrahydrofuran. Fluorinatedsolvents such as nonafluorobutylmethyl ether and fluorinated solventsavailable as HFE-7100, supplied by 3M Innovative Products andperfluorinated ethers supplied by Solvay Solexis under the trademarkGALDEN are preferred for use with the fluorinated material. Thefluorinated solvents can be used in admixtures with the other solventsmentioned above. The fluorinated solvents or diluents are different fromthe fluorinated materials in that the fluorinated solvents or diluentsare not film formers, whereas the fluorinated materials are. Preferably,the vapor pressure of the diluent is high, permitting rapid evaporationat room temperature (20-25° C.). The overlayer material can be dissolvedeasily upon adding the overlayer material to the diluent.

The solution of the overlayer material can be applied to the surface ofthe optical article by dipping, rolling, spraying or wiping. Afterapplication of the overlayer material, the diluent is permitted toevaporate, with or without wiping during evaporation, preferably atambient temperature, or optionally by the application of heat.

The resultant layer typically is thin, having a thickness of about10-100 nanometers or less. The fluorinated overlayers are hydrophobic,having a water contact angle greater than 70°, typically from 75-130°.The water contact angle can be determined using a contact anglegoniometer such as a TANTEC contact angle meter Model CAM-MICRO.

EXAMPLES

The following examples show various coated articles and methods fortheir preparation in accordance with the invention. All parts are byweight unless otherwise indicated.

Example 1

One milliliter of a 0.25% solution of tantalum isopropoxide inisopropanol was dispensed onto a tissue (“Kimwipe” manufactured byKimberly Clark) and rubbed on a polycarbonate lens which had apolysiloxane-based hardcoat for five seconds. Then, one milliliter of a0.2% solution of poly(hexafluoropropyleneoxide)-monophosphonic acidp(HFPO)PA in 5% HFE-7100 (3M Innovative Products), 94% Soltrol-10 (CPChem) and 1% orange oil fragrance (Citrus and Allied) was sprayed ontothe tantalum alkoxide-coated lens surface. Over a period of 30 seconds,the solvent layer began to repel from the lens surface as thefluoropolymer coating reacted with the tantalum alkoxide. Any visiblyremaining coating or solvent was then gently wiped from the surfaceusing a microfiber cloth (Hilco Optiwipe). Water contact angle (WCA)measurements were taken initially, and after abrading the surface with amicrofiber cloth (Hilco Optiwipe) at 150 g/cm² (Table 1).

To show that the organotantalum coating was still active after abrasion,the p(HFPO)PA coating was reapplied and the WCA increased back to theinitial level (Table 1).

Example 2 (Comparative)

One milliliter of a 0.25% solution of aluminum isopropoxide inisopropanol was dispensed onto a tissue (“Kimwipe” manufactured byKimberly Clark) and rubbed on a polycarbonate lens which had apolysiloxane-based hardcoat for five seconds. Then, one milliliter of a0.2% solution of poly(hexafluoropropyleneoxide)-monophosphonic acid in5% HFE-7100 (3M Innovative Products), 94% ethanol (Univar) and 1% orangeoil fragrance (Citrus and Allied) was sprayed onto the aluminumalkoxide-coated lens surface. Over a period of 30 seconds, the solventlayer began to repel from the lens surface as the fluoropolymer coatingreacted with the aluminum alkoxide layer. Any visibly remaining coatingor solvent was then gently wiped from the surface using a microfibercloth (Hilco Optiwipe). Water contact angle measurements were takeninitially, and after abrading the surface with a microfiber cloth (HilcoOptiwipe) at 150 g/cm² (Table 1).

To show that the organoaluminum coating was inactive after abrasion, thep(HFPO)PA coating was reapplied and the WCA did not increase (Table 1).

Example 3 (Comparative)

One milliliter of a 0.25% solution of zirconium propoxide in isopropanolwas dispensed onto a tissue (“Kimwipe” manufactured by Kimberly Clark)and rubbed on a polycarbonate lens which had a polysiloxane-basedhardcoat for five seconds. Then, one milliliter of a 0.2% solution ofpoly(hexafluoropropyleneoxide)-monophosphonic acid in 5% HFE-7100 (3MInnovative Products), 94% ethanol (Univar) and 1% orange oil fragrance(Citrus and Allied) was sprayed onto the zirconium alkoxide-coated lenssurface. Over a period of 30 seconds, the solvent layer began to repelfrom the lens surface as the fluoropolymer coating reacted with thezirconium alkoxide layer. Any visibly remaining coating or solvent wasthen gently wiped from the surface using a microfiber cloth (HilcoOptiwipe). Water contact angle measurements were taken initially, andafter abrading the surface with a microfiber cloth (Hilco Optiwipe) at150 g/cm² (Table 1).

To show that the organozirconium coating was inactive after abrasion,the p(HFPO)PA coating was reapplied and the WCA did not increase (Table1).

Example 4 (Comparative)

One milliliter of a 0.5% solution of titanium n-butoxide in isopropanolwas dispensed onto a tissue (“Kimwipe” manufactured by Kimberly Clark)and rubbed on a polycarbonate lens which had a polysiloxane-basedhardcoat for five seconds. Then, one milliliter of a 0.2% solution ofpoly(hexafluoropropyleneoxide)-monophosphonic acid in 5% HFE-7100 (3MInnovative Products), 94% ethanol (Univar) and 1% orange oil fragrance(Citrus and Allied) was sprayed onto the titanium alkoxide-coated lenssurface. Over a period of 30 seconds, the solvent layer began to repelfrom the lens surface as the fluoropolymer coating reacted with thetitanium alkoxide layer. Any visibly remaining coating or solvent wasthen gently wiped from the surface using a microfiber cloth (HilcoOptiwipe). Water contact angle measurements were taken initially, andafter abrading the surface with a microfiber cloth (Hilco Optiwipe) at150 g/cm² (Table 1).

To show that the organotitanium coating was inactive after abrasion, thep(HFPO)PA coating was reapplied and the WCA did not increase (Table 1).

Example 5 (Comparative)

In this example, no organometallic coating step was employed. Onemilliliter of a 0.2% solution ofpoly(hexafluoropropyleneoxide)-monophosphonic acid in 5% HFE-7100 (3MInnovative Products), 94% ethanol (Univar) and 1% orange oil fragrance(Citrus and Allied) was sprayed onto a polycarbonate lens which had apolysiloxane-based hardcoat. The solvent was allowed to evaporate (30seconds), and any visibly remaining coating or solvent was then gentlywiped from the surface using a microfiber cloth (Hilco Optiwipe). Watercontact angle measurements were taken initially, and after abrading thesurface with a microfiber cloth (Hilco Optiwipe) at 150 g/cm² (Table 1).

TABLE 1 Abrasion Testing² Initial 10 30 50 100 250 Example Coating WCA¹cycles cycles cycles cycles cycles Reapply 1 p(HFPO)PA 110 109 106 104102 100 110 2 p(HFPO)PA 107 105 97 90 N/A N/A 87 3 p(HFPO)PA 112 106 9790 N/A N/A 85 4 p(HFPO)PA 113 110 100 90 N/A N/A 85 5 p(HFPO)PA 85 N/AN/A N/A N/A N/A N/A ¹Water contact angle determined using a contactangle Goniometer TANTEC Contact Angle Meter, Model CAM-MICRO. ²Abrasiontesting was done by rubbing back and forth (1 cycle) with a microfibercloth at a pressure of about 150 g/cm².

The invention is now set forth in the following claims.

1. A coated article comprising: a) a substrate and adhered to thesubstrate surface b) an organometallic film comprising a polymeric metaloxide with alkoxide and hydroxyl groups that covalently bond to thesubstrate and in which the metal has electrons in the f orbital or isniobium; c) adhered to the organometallic film a different film derivedfrom an organophosphorus acid that has groups reactive with the alkoxideand hydroxyl groups.
 2. The coated article of claim 1 in which thesubstrate is a polymer selected from polycarbonate, polyurethane,polyester, polyepoxides, acrylic polymers and copolymers andpolysiloxanes.
 3. The coated article of claim 1 in which the metal isselected from La, Hf, Ta and W. 4-6. (canceled)
 7. The coated article ofclaim 1 in which the organophosphorus acid is selected from a phosphoricacid, a phosphonic acid, a phosphinic acid including derivativesthereof.
 8. The coated article of claim 7 in which the organophosphorusacid or derivative thereof is a fluorinated material.
 9. The coatedarticle of claim 1 in which the coated article is eyewear.
 10. Thecoated article of claim 1 in which the coated article is anelectrooptical article.
 11. A method of depositing an organometalliccoating to a substrate comprising: (a) contacting the surface of thesubstrate with a metal alkoxide and in which the metal has electrons inthe f orbital or is niobium so as to deposit a film on the substratesurface, (b) exposing the film to conditions sufficient to form apolymeric metal oxide with alkoxide and hydroxyl ligands (c) applying tothe film of (b) a different film derived from an organophosphorus acidthat has groups reactive with the alkoxide and hydroxyl groups.
 12. Themethod of claim 11 in which the film (b) is exposed to conditionsresulting in hydrolysis and self-condensation of the alkoxide group. 13.The method of claim 12 in which the film (b) is exposed to amoisture-containing atmosphere.
 14. The method of claim 11 in which themetal is selected from La, Hf, Ta and W.
 15. The method of claim 11 inwhich the substrate is selected from a metal, metal oxide, metalloid,polymer, ceramic and glass.
 16. The method of claim 11 in which thesurface of the substrate prior to deposition contains oxide and/orhydroxyl groups.
 17. The method of claim 16 in which the polymeric metaloxide is covalently bonded to the substrate.
 18. The method of claim 17in which the covalent bond is formed through reaction of the surfaceoxide and/or hydroxyl groups with the alkoxide and/or hydroxyl groupsassociated with the polymeric metal oxide. 19-20. (canceled)
 21. Themethod of claim 11 in which the organophosphorus acid is a phosphonicacid.
 22. An organometallic film of the structure[M(O)_(x)(OH)_(y)(OR)_(z)]_(n) in which M is a metal having electrons inthe f orbital or is niobium; R is an alkyl group containing from 1 to 30carbon atoms; x+y+z=V, the valence of M; x is at least 1; y is at least1; z is at least 1; x=V−y−z; y=V−x−z; z=V−x−y; n is greater than
 2. 23.The organometallic film of claim 22 in which the metal is selected fromLa, Hf, Ta and W.
 24. The organometallic film of claim 23, which has adifferent film deposited thereon.
 25. A coated article comprising: a) asubstrate and adhered to the substrate surface b) an organometallic filmof the structure [M(O)_(x)(OH)_(y)(OR)_(z)]_(n) in which M is a metalhaving electrons in the f orbital or is niobium; R is an alkyl groupcontaining from 1 to 30 carbon atoms; x+y+z=V, the valence of M; x is atleast 1; y is at least 1; z is at least 1; x=V−y−z; y=V−x−z; z=V−x−y; nis greater than
 2. 26. The coated article of claim 25 in which thesubstrate is a polymer selected from polycarbonate, polyurethane,polyester, polyepoxides, acrylic polymers and copolymers andpolysiloxanes.
 27. The coated article of claim 25 in which the metal isselected from La, Hf, Ta and W.
 28. The coated article of claim 25 inwhich the coated article is eyewear.
 29. The coated article of claim 25in which the coated article is an electrooptical article.